18164-03-9

Upstream product

• 98-13-5 Phenyltrichlorosilane 
• 694-53-1 phenylsilane 
• 780-69-8 triethoxyphenylsilane 

Downstream Products

• 93698-11-4 3-deuterio-1,3-diphenyl-1-propanone 
• 1015477-65-2 PhCH₂OSiH₂Ph 

Relevant academic research and scientific papers

Catalytic N-Si coupling as a vehicle for silane dehydrocoupling: Via α-silylene elimination

Exploration of (N3N)ZrNMe2 (1, N3N = N(CH2CH2NSiMe3)33-) as a catalyst for the cross-dehydrocoupling or heterodehydrocoupling of silanes and amines suggested silylene reactivity. Further studies of the catalysis and stoichiometric modeling reactions hint at α-silylene elimination as the pivotal mechanistic step, which expands the 3p elements known to engage in this catalysis and provides a new strategy for the catalytic generation of low-valent fragments.

Vibrational spectra and structure of some silicon containing compounds-IV1 1 For Part III, see J. Mol. Struct. 6, 315 (1970). Normal vibrations and free rotation in phenylsilane

The i.r. spectra of liquid and gaseous phenylsilane and gaseous phenylsilane-d3 have been recorded from 3500 to 33 cm-1. The Raman spectra of the liquids have also been recorded and depolarization values have been measured. The vapor

H/D Exchange of Organosilanes catalysed by Heterogenised Zirconium Hydride Complexes

Silica supported zirconium hydride complexes activate stoichiometrically and catalytically the Si-H bond of primary, secondary and tertiary organosilanes, R4-xSiHx, R = alkyl, aryl.

Well-defined molecular magnesium hydride clusters: Relationship between size and hydrogen-elimination temperature

A new tetranuclear magnesium hydride cluster, [{NN-(MgH)2} 2], which was based on a N-N-coupled bis-β-diketiminate ligand (NN2-), was obtained from the reaction of [{NN-(MgnBu) 2}2] with PhSiH3. Its crystal structure reveals an almost-tetrahedral arrangement of Mg atoms and two different sets of hydride ions, which give rise to a coupling in the NMR spectrum (J=8.5 Hz). To shed light on the relationship between the cluster size and H2 release, the thermal decomposition of [{NN-(MgH)2}2] and two closely related systems that were based on similar ligands, that is, an octanuclear magnesium hydride cluster and a dimeric magnesium hydride species, have been investigated in detail. A lowering of the H2-desorption temperature with decreasing cluster size is observed, in line with previously reported theoretical predictions on (MgH2)n model systems. Deuterium-labeling studies further demonstrate that the released H2 solely originates from the oxidative coupling of two hydride ligands and not from other hydrogen sources, such as the β-diketiminate ligands. Analysis of the DFT-computed electron density in [{NN-(MgH)2}2] reveals a counterintuitive interaction between two formally closed-shell H - ligands that are separated by 3.106 A. This weak interaction could play an important role in H2 desorption. Although the molecular product after H2 release could not be characterized experimentally, DFT calculations on the proposed decomposition product, that is, the low-valence tetranuclear Mg(I) cluster [(NN-Mg2)2], predict a structure with two almost-parallel, localized Mg-Mg bonds. As in a previously reported β-diketiminate MgI dimer, the Mg-Mg bond is not characterized by a bond critical point, but instead displays a local maximum of electron density midway between the atoms, that is, a non-nuclear attractor (NNA). Interestingly, both of the NNAs in [(NN-Mg2)2] are connected through a bond path that suggests that there is bonding between all four MgI atoms. Size matters: The temperature that is required for the elimination of H2 in magnesium hydride clusters is dependent on the cluster size (see scheme). Detailed experimental and/or theoretical data for magnesium hydride and magnesium(I) clusters are reported. Copyright

Synthesis of phenylsilocane tritium-labeled at the benzene ring

A strategy for synthesis of the 2-phenyl-2-hydro-1,3-oxa-6-aza-2-silacyclooctane doubly tritium-labeled (2,4- or 2,6-) at the benzene ring has been elaborated. The products are sources of the silyl cations having the atrane structure.

Titanocene(III)-Catalyzed Precision Deuteration of Epoxides

We describe a titanocene(III)-catalyzed deuterosilylation of epoxides that provides β-deuterated anti-Markovnikov alcohols with excellent D-incorporation, in high yield, and often excellent diastereoselectivity after desilylation. The key to the success of the reaction is a novel activation method of Cp2TiCl2 and (tBuC5H4)2TiCl2 with BnMgBr and PhSiD3 to provide [(RC5H4)2Ti(III)D] without isotope scrambling. It was developed after discovering an off-cycle scrambling with the previously described method. Our precision deuteration can be applied to the synthesis of drug precursors and highlights the power of combining radical chemistry with organometallic catalysis.

Nickel-Catalyzed Hydrosilylation of Terminal Alkenes with Primary Silanes via Electrophilic Silicon-Hydrogen Bond Activation

We report a simple and effective nickel-based catalytic system, NiCl2·6H2O/tBuOK, for the electrophilically activated hydrosilylation of terminal alkenes with primary silanes. This protocol provides excellent performance under mild reaction conditions: ex

Hydrosilane-Mediated Electrochemical Reduction of Amides

Electrochemical reduction of amides was achieved by using a hydrosilane without any toxic or expensive metals. The key reactive ketyl radical intermediate was generated by cathodic reduction. Continuous reaction with anodically generated silyl radicals or zinc bromide resulted in chemoselective deoxygenation to give the corresponding amines.

Specific Z-Selectivity in the Oxidative Isomerization of Allyl Ethers to Generate Geometrically Defined Z-Enol Ethers Using a Cobalt(II)(salen) Complex Catalyst

Enol ether structural motifs exist in many highly oxygenated biologically active natural products and pharmaceuticals. The synthesis of the geometrically less stable Z-enol ethers is challenging. An efficient Z-selective oxidative isomerization process of allyl ethers catalyzed by a cobalt(II) (salen) complex using N-fluoro-2,4,6-trimethylpyridinium trifluoromethanesulfonate (Me3NFPY?OTf) as an oxidant has been developed. Thermodynamically less stable Z-enol ethers were prepared in excellent yields with high geometric control. This methodology also demonstrates the effectiveness in controlling the Z-selective isomerization reaction of diallyl ethers at room temperature. This catalytic system provides an alternative pathway to extend the traditional reductive isomerization of allyl ethers.

Iron-catalyzed protodehalogenation of alkyl and aryl halides using hydrosilanes

A simple and efficient iron-catalyzed protodehalogenation of alkyl and aryl halides using phenylhydrosilane is disclosed. The reaction utilizes FeCl3 without the requirement of ligands. Unactivated alkyl and aryl halides were successfully reduced in good yields; sterically hindered tertiary halides were also reduced including the less reactive chlorides. The scalability of this methodology was demonstrated by a gram-scale synthesis with a catalyst loading as low as 0.5 mol%. Notably, disproportionation of phenylsilane leads to diphenylsilane that further reduces the halides. Preliminary mechanistic studies revealed a non-radical pathway and the source of hydrogen is PhSiH3via deuterium labeling studies. Our methodology represents simplicity and provides a good alternative to typical tin, aluminum and boron hydride reagents.